EP0321462B1 - Lubricant and fuel additives derived from o,o-dialkyldithiophosphoric acid and a norbornyl reactant - Google Patents

Lubricant and fuel additives derived from o,o-dialkyldithiophosphoric acid and a norbornyl reactant Download PDF

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Publication number
EP0321462B1
EP0321462B1 EP87904481A EP87904481A EP0321462B1 EP 0321462 B1 EP0321462 B1 EP 0321462B1 EP 87904481 A EP87904481 A EP 87904481A EP 87904481 A EP87904481 A EP 87904481A EP 0321462 B1 EP0321462 B1 EP 0321462B1
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EP
European Patent Office
Prior art keywords
moiety
hydrocarbyl
compound
imide
alkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP87904481A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0321462A1 (en
Inventor
Richard Michael Lange
William Charles Tritt
Stephen Augustine Di Biase
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lubrizol Corp
Original Assignee
Lubrizol Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lubrizol Corp filed Critical Lubrizol Corp
Priority to AT87904481T priority Critical patent/ATE87027T1/de
Publication of EP0321462A1 publication Critical patent/EP0321462A1/en
Application granted granted Critical
Publication of EP0321462B1 publication Critical patent/EP0321462B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
    • C07F9/165—Esters of thiophosphoric acids
    • C07F9/177—Esters of thiophosphoric acids with cycloaliphatic alcohols
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/26—Organic compounds containing phosphorus
    • C10L1/2633—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond)
    • C10L1/265—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond) oxygen and/or sulfur bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
    • C10M137/10—Thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
    • C10M137/10—Thio derivatives
    • C10M137/105—Thio derivatives not containing metal
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M173/00—Lubricating compositions containing more than 10% water
    • C—CHEMISTRY; METALLURGY
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    • C10M173/00—Lubricating compositions containing more than 10% water
    • C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/02—Water
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
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    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/06—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing conjugated dienes
    • C—CHEMISTRY; METALLURGY
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    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/086—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type polycarboxylic, e.g. maleic acid
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
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    • C10M2215/082—Amides containing hydroxyl groups; Alkoxylated derivatives
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    • C10M2215/28—Amides; Imides
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    • C10M2217/024—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amido or imido group
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    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/046—Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine monomers
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    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/06—Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
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    • C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
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    • C10M2219/046—Overbasedsulfonic acid salts
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/046—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for traction drives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/08—Hydraulic fluids, e.g. brake-fluids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/251—Alcohol-fuelled engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • C10N2040/28—Rotary engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/01—Emulsions, colloids, or micelles
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2070/00—Specific manufacturing methods for lubricant compositions
    • C10N2070/02—Concentrating of additives

Definitions

  • This invention relates to novel additives for functional fluids that are derived from a norbornyl reactant and O,O-dialkyldithiophosphoric acids. It has been discovered that these additives improve the extreme pressure, antiwear and antioxidant properties of functional fluids, e.g., lubricants and fuels, for use in internal combustion engines and the machinery of motorized vehicles.
  • functional fluids e.g., lubricants and fuels
  • O,O-Dialkyldithiophosphoric acid adducts of a norbornene reactant have been disclosed in the art.
  • various dialkyldithiophosphoric acid esters of norbornene reactants are disclosed as possessing good insecticidal, fungicidal and miticidal properties. It is also disclosed that these compounds have properties rendering them useful as corrosion inhibitors, plasticizing agents, lubricating oil additives and flotation agents, etc.
  • U.S. Patent 3,962,105 discloses various diesters and/or ester lactones of norbornene and norbornane systems which are useful as seal swell additives.
  • a transmission fluid comprising an alkylene oxide adduct of a phosphosulfurized N-(hydroxyalkyl) alkenyl succinimide.
  • dialkyldithiophosphoric acid esters of succinimides are disclosed as being adaptable for various uses such as insecticides, fungicides, plasticisers, corrosion inhibitors, flotation agents, and petroleum additives.
  • a lubricating composition comprising a major amount of an oil of lubricating viscosity and minor amount of a compound of the formula: wherein R is, independently, alkyl or aryl and X and Y are independently selected from hydrogen, hydrocarbyl carboxy, a N-substituted carboxamide moiety, a thio- or dithiocarbamate moiety, a thioamide moiety, a thio acid or ester moiety, a hydrocarbyl phosphorus containing radical, or together are imide or N-hydrocarbyl substituted imide, provided that when X is alkyl carboxy, Y is not alkyl carboxy or hydrogen, and X and Y are not both hydrogen.
  • a lubricant additive comprising the compound of the present invention.
  • a concentrate for formulating lubricating compositions comprising from 1% to 99% by weight of a normally liquid, substantially inert organic solvent/diluent and at least one compound of the present invention.
  • a lubricating composition comprising a major amount of an oil of lubricating viscosity and a minor amount of at least one compound or at least one concentrate of the present invention.
  • a method for improving the load bearing properties of a lubricating composition comprising admixing with a major amount of a lubricating composition, a minor amount of the compound or concentrate of the present invention.
  • an aqueous functional fluid comprising a minor amount of at least one compound of the present invention.
  • a grease composition comprising a minor amount of at least one compound of the present invention.
  • the norbornyl dialkyldithiophosphate adducts of the present invention may be represented by the following formula:
  • hydrocarbyl or “hydrocarbon-based” denote a radical having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character within the context of this invention.
  • radicals include the following:
  • alkyl-based radical alkyl-based radical
  • aryl-based radical aryl-based radical
  • radicals are usually hydrocarbon and especially lower hydrocarbon, the word "lower” denoting radicals containing up to ten (10) carbon atoms. They are preferably lower alkyl or aryl radicals, most often alkyl.
  • the preparation of the norbornyl reactant most preferably used to react with the dialkyldithiophosphoric acid, i.e., 5-norbornene-2,3-dicarboxylic anhydride is described in Onishchenko, Diene Synthesis (translation from the Russian by Israel Program for Scientific Translations, Jerusalem, 1964), Daniel Davey and Company, Publisher, New York (1964), pages 38, 47, 48-50 and references cited therein.
  • the preparation of 5-morbornene-2,3-dicarboxylic anhydride involves the Diels-Alder reaction or dicyclopentadiene with maleic anhydride. All isomer is forms of the reaction products of the present invention are intended to be within the scope of this invention. For example, the above-referenced process may result in the production of both the exo and endo forms of this molecule. Both isomers are intended to be within the scope of the present invention.
  • the above norbornene dicarboxylic anhydride reactant is then reacted with a O,O-dialkyldithiophosphoric acid of the formula: (RO)2P(S)SH to form a norbornyl dialkydithiophosphate, the structure of which may be represented by the following formula:
  • the alkyl group R of the dithiophosphoric acid ester may contain 1 to about 30 carbon atoms and preferably 3 to about 12 carbon atoms.
  • the anhydride group on the norbornyl ring may be in the endo or ego position or there may be mixtures thereof.
  • the above compound represented by formula II
  • X and Y of formula I may be a primary or secondary C2 to C200 alkyl, aralkyl, aryl or alkylaryl (linear or branched), and may contain unsaturation, halogen or heteroatoms, alicyclic or heterocyclic rings, fused rings.
  • -OH -NR2
  • carbonyl in a diversity of structures (ester, carboxylic acid, aldehyde, ketone, amide or imide), corresponding thiocarbonyl moieties, thioesters, thiolesters, dithioesters, thio- and dithiocarbamates), halogen, alkoxy-, alkylthio, mercapto,
  • the half-ester acids may be used directly, or they may be converted to salts of metals selected from Group IA and IIA of the periodic table, as well as from the various transition series; which include Zn, Cd, Sn, Pb, Sb, Cu, Ni, Mn, Co, Fe, Cr, Ti and Zr, also the lanthanides, and the complex uranyl cation, UO2+2.
  • Hydrolysis of the anhydride ring of structure II produces a dicarboxylic acid which may be oleophilic depending on the size and nature of the hydrocarbyl groups of the dithiophosphate ester portion of the molecule.
  • this hydrolysis product may be hydrophilic if the hydrocarbyl groups of the dithiophosphate ester are lower alkyl.
  • the hydrophilic product may be rendered water soluble by forming the corresponding salts of Group I and II metals, as well as salts of many of the metals discussed above.
  • Salts of I may be made more soluble in oil or in aqueous solution by using appropriate alkyl (R) groups, and by amine complexation, where this is feasible (as with transition metal ions).
  • the above compounds may be prepared, in general, by reacting the particular reagent, e.g., an alcohol, an amine, an ester, a thiol or the like, with the anhydride II intermediate at an elevated temperature to obtain the desired product.
  • a monoester of II wherein Y in formula I is an acid group and X is an ester group may be prepared as illustrated below. wherein R and R' are independently hydrocarbyl.
  • Diesters of II may be prepared, for example, by condensing II with two moles of alcohol, R'OH, generally using an acidic catalyst, such as methanesulfonic acid or p-toluenesulfonic acid. wherein R' and R are independently hydrocarbyl.
  • nitrogen, sulfur and phosphorus-containing derivatives are also within the scope of the present invention.
  • X and Y of formula I above are amide, urethane, thioamide, thioester, dithioester, mercapto, hydrocarbyl containing dithiocarbanate, phosphate, phosphite, phosphonate, dithiophosphate and/or phosphoramide or together are imide or N-hydrocarbyl substituted imide.
  • heteroatom products may be derived from hydrocarbyl amines and amides; hydrocarbyl thiols; phosphorus containing, alcohols, esters and carbonates; hydrocarbyl alcohols; hydrocarbyl carbonates; hydrocarbyl carboxylic acids, anhydrides and esters; and hydrocarbyl halides.
  • the reagents that may be used to react with II include alkyl, aryl, alkenyl and heterocyclic amines such as methylamine, dimethylamine, amiline and substituted amilines, aminotriazoles, aminothiazoles, aminophenols,ethanolamine, diethanolamine, triethanolamine, morpholine, stearylamine, oleylamine, palmylamine, lauryl-amine, eicosylamine, and the like; alkyl and alkenyl phosphites, phosphates and phosphonates such as hydroxy-methyl dibutyl phosphonate; alcohols such as ethanol, butanol, phenol, ethylene glycol, pentarylthritol as well as alkoxylated phenols, alkoxylated alcohols, alkoxylated amines, and the like; thiols such as ethanethiol, octanethiol, butanethiol and the like.
  • reaction with the anhydride of structure II would be expected to produce first an amidic acid of structure I, wherein X and Y. are, respectively, -CO2H and -C(O)NHR. Heating this product at moderate temperatures (e.g., approximately 85° to 135°C), causes the amidic acid to cyclize to the five-membered cyclic imide illustrated below where R and R' are, independently, hydrocarbyl.
  • exo or endo forms of the anhydride of formula II will form the corresponding exo or endo forms of the imides of formula III, providing that the compounds are not heated to extraordinarily high temperatures (i.e., greater than 160°C).
  • reaction of the above-listed reagents with the norbornyl anhydride (II) is conducted under condensation conditions recognized in the art as discussed above to illustrate the preferred method for the preparation of the monoester, diester and other such derivatives.
  • the reaction is carried out in the presence of an acid or basic catalyst and/or at an elevated temperature.
  • the product produced may otherwise be described as the reaction product of:
  • esters, half-esters, amidic acids or imides are also feasible and in some instances may be more desirable for the preparation of certain of the structures which may contain specific groups.
  • One such other method for preparing esters, half-esters, amidic acids or imides is to first form the corresponding esters, half-esters, amidic acids or imides of 5-norbornene-2,-3-dicarboxylic anhydride, itself, followed by the reaction of the residual olefinic site with an O,O-dialkyl dithiophosphoric acid to form the desired saturated adducts.
  • a reaction flask was charged with 911 grams of 5-norbornene-2,3-dicarboxylic anhydride and 750 ml of toluene, heated to 70°C to effect dissolution. After purging the system with inert nitrogen gas, 1980 grams of O.O-di-isooctyl dithiophosphoric acid was added in a continuous manner at 80-90°C over a period of 2 hours. The homogeneous solution was held at 90°C or an additional 5 hours with stirring under a slow nitrogen sparge, during which time the strong acid number (bromphenol blue indicator) of the reaction mixture decreased rapidly.
  • the homogeneous solution was held at 90°C or an additional 5 hours with stirring under a slow nitrogen sparge, during which time the strong acid number (bromphenol blue indicator) of the reaction mixture decreased rapidly.
  • a reaction flask was charged with 570 grams of the product of Example 1 and 300 ml of toluene. The mixture was stirred under nitrogen while 61 grams of ethanolamine was added to the solution. The temperature rose rapidly from 25°C to 60°C over 6 min. The solution was heated at gentle reflux (ca 110°C) for 3 hours while 16.2 ml of water (90% of theory) was collected.
  • a reaction flask was charged with 358 grams of the anhydride product of Example 1 and 142 grams of dibutyl hydroxymethylphosphonate, previously prepared by base-catalyzed condensation of paraformaldehyde and dibutyl hydrogen phosphite.
  • the reaction mixture was stirred under nitrogen, and heated in stages: 85°C for 2 hours; 100°C for 2 hours; 120°C for 2.5 hours.
  • the mixture was filtered through diatomaceous earth to give 480 grams of product.
  • a reaction flask was charged with 489 grams of the product of Example 1, 400 ml of toluene, 160 grams of ethylene glycol, and 1 gram of p-toluenesulfonic acid catalyst.
  • the reaction mixture was stirred and heated to gentle reflux with slow nitrogen sparging, and water of condensation was removed over a period of 8 hours; a total of 16.6 ml of water was evolved at this point (100% of theory) for the formation of a diester of the cyclic dicarboxylic anhydride.
  • the reaction mixture was cooled to room temperature and washed with two-500ml portions of water.
  • the compounds of the present invention have been found to be useful extreme pressure agents and antiwear agents as well as antioxidants for lubricating compositions.
  • the compounds of the present invention may also find use as additives for other such functional fluids as automatic transmission fluids and hydraulic fluids.
  • the compounds of the invention may be formulated with a lubricating oil or an automatic transmission fluid or the like by the direct blending of the composition with the particular oil or functional fluid to be formulated.
  • the lubricating oil or other functional fluid may also be formulated with compounds of the present invention in the form of a concentrate.
  • Such a concentrate may be prepared by adding 1% to 99% by weight of at least 1 compound of the present invention to a substantially inert, normally liquid organic diluent or solvent such as benzene, toluene, xylene, petroleum naphtha, mineral oil, ethyleneglycol-mono-methylether or the like.
  • the amount of these additives formulated with a particular lubricant may vary over a wide range and must be an amount to effectively impart extreme pressure and antiwear properties in the lubricant. As a preferred amount, the additive may range from 0.01 weight percent to about 10 weight percent of the formulated lubricant. In a most preferred embodiment, the amount may range from about 0.1 weight percent to about 5 weight percent of the formulated lubricant.
  • compositions of the present invention formulated with the particular functional fluid may contain other additives and chemistries such as dispersants, antioxidants, and the like.
  • additives and chemistries include, for example, detergents and dispersants of the ash-producing or ashless type, corrosion- and oxidation-inhibiting agents, pour point depressing agents, auxiliary extreme pressure agents, color stabilizers and anti-foam agents.
  • a preferred dispersant according to the present invention is at least one substituted succinic acid or derivative thereof consisting of substituent groups wherein the substituent groups are derived from polyalkylene, said polyalkylene being characterized by a Mn value of 500 to about 10,000 and a Mw/Mn value of 1.0 to about 4.0.
  • the norbornene adduct additives of the present invention are useful in both mineral and synthetic lubricating oils and greases.
  • Synthetic oils include polyolefin oils (e.g., polybutene oil, decene oligomer, and the like), synthetic esters (e.g., dinonyl sebacate, trioctanoic acid ester of trimethyolpropane, and the like), polyglycol oils, and the like.
  • Greases are made from these oils by adding a thickening agent such as sodium, calcium, lithium, or aluminum salts of fatty acids such as stearic acid.
  • the oils and greases of the present invention are prepared by blending an amount of the carbamate additive of the present invention sufficient to impart extreme pressure properties and antiwear properties into the oil or grease.
  • a useful concentration may range from about 0.1 to about 5 weight percent.
  • compositions according to this invention are listed in the following table.
  • the invention also includes aqueous compositions characterized by an aqueous phase with at least one amine and/or metal salt of at least one dimer or polymer of the present invention dispersed or dissolved in said aqueous phase.
  • this aqueous phase is a continuous aqueous phase although, in some embodiments, the aqueous phase can be a discontinuous phase.
  • These aqueous compositions usually contain at least about 25% by weight water.
  • Such aqueous compositions encompass both concentrates containing about 25% to about 80% by weight, preferably from about 40% to about 65% water; and water-based functional fluids containing generally greater than about 80% by weight of water.
  • the concentrates generally contain from about 10% to about 90% by weight of at least one of the norbornene adduct additives of the invention.
  • the water-based functional fluids generally contain from about 0.05% to about 15% by weight of the norbornene adduct materials of the invention.
  • the concentrates generally contain less than about 50%, preferably less than about 25%, more preferably less than about 15%, and still more preferably less than about 6% hydrocarbon oil.
  • the water-based functional fluids generally contain less than about 15%, preferably less than about 5%, and more preferably less than about 2% hydrocarbon oil.
  • These concentrates and water-based functional fluids can optionally include other conventional additives commonly employed in water-based functional fluids.
  • additives include surfactants; thickeners; oil-soluble, water-insoluble functional additives such as antiwear agents, extreme pressure agents, dispersants, etc.; and supplemental additives such as corrosion-inhibitors, shear stabilizing agents, bactericides, dyes, water-softeners, odor masking agents, anti-foam agents and the like.
  • the concentrates are analogous to the water-based functional fluids except except that they contain less water and proportionately more of the other ingredients.
  • the concentrates can be converted to water-based functional fluids by dilution with water. This dilution is usually done by standard mixing techniques. This is often a convenient procedure since the concentrate can be shipped to the point of use before additional water is added. Thus, the cost of shipping a substantial amount of the water in the final water-based functional fluid is saved. Only the water necessary to formulate the concentrate (which is determined primarily be ease of handling and convenience factors), need be shipped.
  • these water-based functional fluids are made by diluting the concentrates with water, wherein the ratio of water to concentrate is usually in the range of about 80:20 to about 99:1 by weight. As can be seen when dilution is carried out within these ranges, the final water-based functional fluid contains, at most, an insignificant amount of hydrocarbon oil.
  • the water-based functional fluids are in the form of solutions while in other embodiments they are in the form of micelle dispersions or microemulsions which appear to be true solutions. Whether a solution, micelle dispersion or microemulsion is formed is dependent, inter alia, on the particular components employed.
  • aqueous compositions including both concentrates and water-based functional fluids, containing other conventional additives commonly employed in water-based functional fluids. These methods comprise the steps of:
  • the concentrate can be formed and then shipped to the point of use where it is diluted with water to form the desired water-based functional fluid.
  • the finished water-based functional fluid can be formed directly in the same equipment used to form the concentrate or the dispersion or solution.
  • the surfactants that are useful in the aqueous compositions of the invention can be of the cationic, anionic, nonionic or amphoteric type. Many such surfactants of each type are know to the art. See, for example, McCutcheon's "Emulsifiers & Detergents," 1981, North American Edition, published by McCutcheon Division, MC Publishing Co., Glen Rock, New Jersey, U.S.A.
  • nonionic surfactant types are the alkylene oxide-treated products, such as ethylene oxide-treated phenols, alcohols, esters, amines and amides. Ethylene oxide/propylene oxide block copolymers are also useful nonionic surfactants. Glycerol esters and sugar esters are also known to be nonionic surfactants.
  • a typical nonionic surfactant class useful with the present invention are the alkylene oxide-treated alkyl phenols such as the ethylene oxide alkyl phenol condensates sold by the Rohm & Haas Company.
  • Triton X-100 which contains an average of 9-10 ethylene oxide units per molecule, has an HLB value of about 13.5 and a molecular weight of about 628.
  • suitable nonionic surfactants are known; see, for example, the aforementioned McCutcheon's as well as the treatise "Non-Ionic Surfactants” edited by Martin J. Schick, M. Dekker Co., New York, 1967.
  • cationic, anionic and amphoteric surfactants can also be used. Generally, these are all hydrophilic surfactants. Anionic surfactants contain negatively charged polar groups while cationic surfactants contain positively charged polar groups. Amphoteric dispersants contain both types of polar groups in the same molecule. A general survey of useful surfactants is found in Kirk-Othmer Encyclopedia of Chemical Technology, Second Edition, Volume 19, page 507 et seq. (1969, John Wiley and Son, New York) and the aforementioned compilation published under the name of McCutcheon's.
  • anionic surfactant types are the widely known carboxylate soaps, organo sulfates, sulfonates, sulfocarboxylic acids and their salts, and phosphates.
  • Useful cationic surfactants include nitrogen compounds such as amine oxides and the well-known quaternary ammonium salts.
  • Amphoteric surfactants include amino acid-type materials and similar types.
  • Various cationic, anionic and amphoteric dispersants are available from the industry, particularly from such companies as Rohm & Haas and Union Carbide Corporation, both of America. Further information about anionic and cationic surfactants also can be found in the texts "Anionic Surfactants," Parts II and III, edited by W. M. Linfield, published by Marcel Dekker, Inc., New York, 1976, and “Cationic Surfactants,” edited by E. Jungermann, Marcel Dekker, Inc., New York, 1976.
  • the concentrates can contain up to about 75% by weight, more preferably from about 10% to about 75% by weight of one or more of these surfactants.
  • the water-based functional fluids can contain up to about 15% by weight, more preferably from about 0.05% to about 15% by weight of one or more of these surfactants.
  • the aqueous compositions of this invention contain at least one thickener for thickening said compositions.
  • these thickeners can be polysaccharides, synthetic thickening polymers, or mixtures of two or more of these.
  • polysaccharides that are useful are natural gums such as those disclosed in "Industrial Gums" by Whistler and B. Miller, published by Academic Press, 1959. Specific examples of such gums are gum agar, guar gum, gum arabic, algin, dextrans, xanthan gum and the like.
  • cellulose ethers and esters including hydroxy hydrocarbyl cellulose and hydrocarbylhydroxy cellulose and its salts.
  • specific examples of such thickeners are hydroxyethyl cellulose and the sodium salt of carboxymethyl cellulose. Mixtures of two or more of any such thickeners are also useful.
  • the thickener used in the aqueous compositions of the present invention be soluble in both cold (10°C) and hot (about 90°C) water. This excludes such materials as methyl cellulose which is soluble in cold water but not in hot water. Such hot-water-insoluble materials, however, can be used to perform other functions such as providing lubricity to the aqueous compositions of this invention.
  • thickeners can also be synthetic thickening polymers.
  • Many such polymers are known to those of skill in the art. Representative of them are polyacrylates, polyacrylamides, hydrolyzed vinyl esters, water-soluble homo- and interpolymers of acrylamidoalkane sulfonates containing 50 mole percent at least of acryloamido alkane sulfonate and other comonomers such as acrylonitrile, styrene and the like.
  • Poly-n-vinyl pyrrolidones, homo-and copolymers as well as water-soluble salts of styrene, maleic anhydride and isobutylene maleic anhydride copolymers can also be used as thickening agents.
  • Preferred thickeners are the water-dispersible reaction products formed by reacting at least one hydrocarbyl-substituted succinic acid and/or anhydride represented by the formula wherein R is a hydrocarbyl group of from about 8 to about 40 carbon atoms, with at least one water-dispersible amine terminated poly(oxyalkylene) or at least one water-dispersible hydroxy-terminated polyoxyalkylene.
  • R prererably has from about 8 to about 30 carbon atoms, more preferably from about 12 to about 24 carbon atoms, still more preferably from about 16 to about 18 carbon atoms.
  • R is represented by the formula wherein R' and R'' are independently hydrogen or straight chain or substantially straight chain hydrocarbyl groups, with the proviso that the total number of carbon atoms in R is within the above-indicated ranges.
  • R' and R'' are alkyl or alkenyl groups.
  • R has from about 16 to about 18 carbon atoms
  • R' is hydrogen or an alkyl group of from 1 to about 7 carbon atoms or an alkenyl group of from 2 to about 7 carbon atoms
  • R'' is an alkyl or alkenyl group of from about 5 to about 15 carbon atoms.
  • the water-dispersible amine terminated poly(oxyalkylene)s are preferably alpha omega diamino poly(oxyethylene)s, alpha omega diamino poly(oxypropylene) poly(oxyethylene) poly(oxypropylene)s or alpha omega diamino propylene oxide capped poly(oxyethylene)s.
  • the amine-terminated poly(oxyalkylene) can also be a urea condensate of such alpha omega diamino poly(oxytheylene)s, alpha omega diamino poly(oxypropylene) poly(oxyethylene) poly(oxypropylene)s or alpha omega diamino propylene oxide capped poly(oxyethylene)s.
  • the amine-terminated poly(oxyalkylene) can also be a polyamine (e.g., triamino, tetramino, etc.) polyoxyalkylene provided it is amine-terminated and it is water-dispersible.
  • water-dispersible amine-terminated poly(oxyalkylene)s that are useful in accordance with the present invention are disclosed in U.S. Patents 3,021,232; 3,108,011; 4,444,566; and RE 31,522. The disclosures of these patents are incorporated herein by reference. Water-dispersible amine terminated poly(oxyalkylene)s that are useful are commercially available from the Texaco Chemical Company under the trade name "Jeffamine.”
  • the water-dispersible hydroxy-terminated polyoxyalkylenes are constituted of block polymers of propylene oxide and ethylene oxide, and a nucleus which is derived from organic compounds containing a plurality of reactive hydrogen atoms.
  • the block polymers are attached to the nucleus at the sites of the reactive hydrogen atoms.
  • these compounds include the hydroxy-terminated polyoxyalkylenes which are represented by the formula wherein a and b are integers such that the collective molecular weight of the oxypropylene chains range from about 900 to about 25,000, and the collective weight of the oxyethylene chains constitute from about 20% to about 90%, preferably from about 25% to about 55% by weight of the compound.
  • hydroxy-terminated polyoxyalkylenes represented by the formula HO(C2H4O) x (C3H6O) y (C2H4O) z H wherein y is an integer such that the molecular weight of the oxypropylene chain is at least about 900, and x and z are integers such that the collective weight of the oxyethylene chains constitute from about 20% to about 90% by weight of the compound.
  • y is an integer such that the molecular weight of the oxypropylene chain is at least about 900
  • x and z are integers such that the collective weight of the oxyethylene chains constitute from about 20% to about 90% by weight of the compound.
  • These compounds preferably have a molecular weight in the range of about 1,100 to about 14,000.
  • Those compounds are commercially available from BASF Wyandotte Corporation under the trade name "Pluronic.”
  • Useful hydroxy-terminated polyoxyalkylenes are disclosed in U.S. Patents 2,674,619 and 2,979,5
  • the reaction between the carboxylic agent and the amine- or hydroxy-terminated polyoxyalkylene can be carried out at a temperature ranging from the highest of the melt temperatures of the reaction components up to the lowest of the decomposition temperatures of the reaction components or products. Generally, the reaction is carried out at a temperature in the range of about 60°C to about 160°C, preferably about 120°C to about 160°C.
  • the ratio of equivalents of carboxylic agent to polyoxyalkylene preferably ranges from about 0.1:1 to about 8:1, preferably about 1:1 to about 4:1, and advantageously about 2:1.
  • the weight of an equivalent of the carboxylic agent can be determined by dividing its molecular weight by the number of carboxylic functions present.
  • the weight of an equivalent of the amine-terminated polyoxyalkylene can be determined by dividing its molecular weight by the number of terminal amine groups present.
  • the weight of an equivalent of the amine-terminated polyoxyalkylene can be determined by dividing its molecular-weight by the number of terminal amine groups present.
  • the number of terminal amine and hydroxyl groups can usually be determined from the structural formula of the polyoxyalkylene or empirically through well-known procedures.
  • the amine/acids and ester/acids formed by the reaction of the carboxylic agent and amine-terminated or hydroxy-terminated polyoxyalkylene can be neutralized with, for example, one or more alkali metals, one or more amines, or a mixture thereof, and thus converted to amide/salts or ester/salts, respectively. Additionally, if these amide/acids or ester/acids are added to concentrates or functional fluids containing alkali metals or amines, amide/salts or ester/salts usually form, in situ.
  • South African Patent 85/0978 discloses the use of hydrocarbyl-substituted succinic acid or anhydride/hydroxy-terminated poly(oxyalkylene) reaction products as thickeners for aqueous compositions.
  • the thickener is formed using an amine-terminated poly(oxyalkylene)
  • the thickening characteristics of said thickener can be enhanced by combining it with at least one surfactant.
  • Any of the surfactants identified above under the subtitle "Surfactants" can be used in this regard.
  • the weight ratio of thickener to surfactant is generally in the range of from about 1:5 to about 5:1, preferably from about 1:1 to about 3:1.
  • the thickener is present in a thickening amount in the aqueous compositions of this invention.
  • the thickener is preferably present at a level of up to about 70% by weight, preferably from about 20% to about 50% by weight of the concentrates of the invention.
  • the thickener is preferably present at a level in the range of from about 1.5% to about 10% by weight, preferably from about 3% to about 6% by weight of the functional fluids of the invention.
  • the functional additives that can be used in the aqueous systems are typically oil-soluble, water-insoluble additives which function in conventional oil-based systems as extreme pressure agents, antiwear agents, load-carrying agents, dispersants, friction modifiers, lubricity agents, etc. They can also function as anti-slip agents, film formers and friction modifiers. As is well known, such additives can function in two or more of the above-mentioned ways; for example, extreme pressure agents often function as load-carrying agents.
  • oil-soluble, water-insoluble functional additive refers to a functional additive which is not soluble in water above a level of about 1 gram per 100 milliliters of water at 25°C, but is soluble in mineral oil to the extent of at least 1 gram per liter at 25°C.
  • These functional additives can also include certain solid lubricants such as graphite, molybdenum disulfide and polytetrafluoroethylene and related solid polymers.
  • These functional additives can also include frictional polymer formers.
  • frictional polymer formers are potential polymer forming materials which are dispersed in a liquid carrier at low concentration and which polymerize at rubbing or contacting surfaces to form protective polymeric films on the surfaces. The polymerizations are believed to result from the heat generated by the rubbing and, possibly, from catalytic and/or chemical action of the freshly exposed surface.
  • a specific example of such materials is dilinoleic acid and ethylene glycol combinations which can form a polyester frictional polymer film.
  • these functional additives are known metal or amine salts of organo sulfur, phosphorus, boron or carboxylic acids which are the same as or of the same type as used in oil-based fluids.
  • such salts are of carboxylic acids of 1 to 22 carbon atoms including both aromatic and aliphatic acids; sulfur acids such as alkyl and aromatic sulfonic acids and the like; phosphorus acids such as phosphoric acid, phosphorus acid, phosphinic acid, acid phosphate esters and analogous sulfur homologs such as the thiophosphoric and dithiophosphoric acid and related acid esters; boron acics include boric acid, acid borates and the like.
  • Useful functional additives also include metal dithiocarbamates such as molybdenum and antimony dithiocarbamates; as well as dibutyl tin sulfide, tributyl tin oxide, phosphates and phosphites; borate amine salts, chlorinated waxes; trialkyl tin oxide, molybdenum phosphates, and chlorinated waxes.
  • the functional additive is a sulfur or chloro-sulfur extreme pressure agent, known to be useful in oil-base systems.
  • Such materials include chlorinated aliphatic hydrocarbons, such as chlorinated wax; organic sulfides and polysulfides, such as benzyl-disulfide, bis-(chlorobenzyl)disulfide, dibutyl tetrasulfide, sulfurized sperm oil, sulfurized methyl ester of oleic acid, sulfurized alkylphenol, sulfurized dipentene, sulfurized terpene, and sulfurized Diels-Alder adducts; phosphosulfurized hydrocarbons, such as the reaction product of phosphorus sulfide with turpentine or methyl oleate; phosphorus esters such as the dihydrocarbon and trihydrocarbon phosphites, i.e., dibutyl phosphite, dih
  • the functional additive can also be a film former such as a synthetic or natural latex or emulsion thereof in water.
  • a film former such as a synthetic or natural latex or emulsion thereof in water.
  • latexes include natural rubber latexes and polystyrene butadienes synthetic latex.
  • the functional additive can also be an anti-chatter or anti-squawk agent.
  • the former are the amide metal dithiophosphate combinations such as disclosed in West German Patent 1,109,302; amine salt-azomethene combinations such as disclosed in British Patent Specification 893,977; or amine dithiophosphate such as disclosed in U.S. Patent 3,002,014.
  • anti-squawk agents are N-acyl-sarcosines and derivatives thereof such as disclosed in U.S. Patents 3,156,652 and 3,156,653; sulfurized fatty acids and esters thereof such as disclosed in U.S. Patents 2,913,415 and 2,982,734; and esters of dimerized fatty acids such as disclosed in U.S. Patent 3,039,967.
  • Mixtures of two or more of any of the afore-described functional additives can also be used.
  • a functionally effective amount of the functional additive is present in the aqueous compositions of this invention.
  • the term "functionally effective amount” refers to a sufficient quantity of an additive to impart desired properties intended by the addition of said additive.
  • an additive is a rust-inhibitor
  • a functionally effective amount of said rust-inhibitor would be an amount sufficient to increase the rust-inhibiting characteristics of the composition to which it is added.
  • the additive is an antiwear agent
  • a functionally effective amount of said antiwear agent would be a sufficient quantity of the antiwear agent to improve the antiwear characteristics of the composition to which it is added.
  • the aqueous systems of this invention often contain at least one inhibitor for corrosion of metals. These inhibitors can prevent corrosion of either ferrous or non-ferrous metals (e.g., copper, bronze, brass, titanium, aluminum and the like) or both.
  • the inhibitor can be organic or inorganic in nature. Usually it is sufficiently soluble in water to provide a satisfactory inhibiting action though it can function as a corrosion-inhibitor without dissolving in water, it need not be water-soluble.
  • Many suitable inorganic inhibitors useful in the aqueous systems of the present invention are known to those skilled in the art. Included are those described in "Protective Coatings for Metals" by Burns and Bradley, Reinhold Publishing Corporation, Second Edition, Chapter 13, pages 596-605.
  • useful inorganic inhibitors include alkali metal nitrites, sodium di- and tripolyphosphate, potassium and dipotassium phosphate, alkali metal borate and mixtures of the same.
  • suitable organic inhibitors are known to those of skill in the art.
  • Specific examples include hydrocarbyl amine and hydroxy-substituted hydrocarbyl amine neutralized acid compound, such as neutralized phosphates and hydrocarbyl phosphate esters, neutralized fatty acids (e.g., those having about 3 to about 22 carbon atoms), neutralized aromatic carboxylic acids (e.g., 4-tertiarybutyl benzoic acid), neutralized naphthenic acids and neutralized hydrocarbyl sulfonates.
  • amines include the alkanol amines such as ethanol amine, diethanolamine. Mixtures of two or more of any of the afore-described corrosion-inhibitors can also be used.
  • the corrosion-inhibitor is usually present in concentrations in which they are effective in inhibiting corrosion of metals with which the aqueous composition comes in contact.
  • Certain of the aqueous systems of the present invention can also contain at least one polyol with inverse solubility in water.
  • polyols are those that become less soluble as the temperature of the water increases. They thus can function as surface lubricity agents during cutting or working operations since, as the liquid is heated as a result of friction between a metal workpiece and work tool, the polyol of inverse solubility "plates out" on the surface of the workpiece, thus improving its lubricity characteristics.
  • the aqueous systems of the present invention can also include at least one bactericide.
  • bactericides are well known to those of skill in the art and specific examples can be found in the afore-mentioned McCutcheon publication "Functional Materials” under the heading "Antimicrobials” on pages 9-20 thereof.
  • these bacterides are water-soluble, at least to the extent to the extent to allow them to function as bactericides.
  • the aqueous systems of the present invention can also include such other materials as dyes, e.g., an acid green dye; water softeners, e.g., ethylene diamine tetraacetate sodium salt or nitrilo triacetic acid; odor masking agents, e.g., citronella, oil of lemon, and the like; and anti-foamants, such as the well-known silicone anti-foamant agents.
  • dyes e.g., an acid green dye
  • water softeners e.g., ethylene diamine tetraacetate sodium salt or nitrilo triacetic acid
  • odor masking agents e.g., citronella, oil of lemon, and the like
  • anti-foamants such as the well-known silicone anti-foamant agents.
  • the aqueous systems of this invention may also include an antifreeze additive where it is desired to use the composition at a low temperature.
  • an antifreeze additive such as ethylene glycol and analogous polyoxyalkylene polyols can be used as antifreeze agents.
  • the amount used will depend on the degree of antifreeze protection desired and will be known to those of ordinary skill in the art.
  • ingredients described above for use in making the aqueous systems of this invention are industrial products which exhibit or confer more than one property on such aqueous compositions.
  • a single ingredient can provide several functions thereby eliminating or reducing the need for some other additional ingredient.
  • an extreme pressure agent such as tributyl tin oxide can also function as a bactericide.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Combustion & Propulsion (AREA)
  • Lubricants (AREA)
  • Liquid Carbonaceous Fuels (AREA)
EP87904481A 1986-07-11 1987-07-02 Lubricant and fuel additives derived from o,o-dialkyldithiophosphoric acid and a norbornyl reactant Expired - Lifetime EP0321462B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87904481T ATE87027T1 (de) 1986-07-11 1987-07-02 Schmiermittel und brennstoffzusatzmittel aus dialkyldithiophosphorsaeure und einem norbornylreaktanten.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US06/884,685 US4729840A (en) 1986-07-11 1986-07-11 Lubricant and fuel additives derived from O,O-dialkyldithiophosphoric acid and a norbornyl reactant
US884685 1986-07-11

Publications (2)

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EP0321462A1 EP0321462A1 (en) 1989-06-28
EP0321462B1 true EP0321462B1 (en) 1993-03-17

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US (1) US4729840A (es)
EP (1) EP0321462B1 (es)
JP (1) JP2614882B2 (es)
AT (1) ATE87027T1 (es)
AU (1) AU603819B2 (es)
CA (1) CA1308727C (es)
DE (1) DE3784937T2 (es)
ES (1) ES2010723A6 (es)
HK (1) HK102793A (es)
IN (1) IN168375B (es)
MX (1) MX163959B (es)
WO (1) WO1988000611A2 (es)
ZA (1) ZA875004B (es)

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Publication number Priority date Publication date Assignee Title
JP2795890B2 (ja) * 1989-04-12 1998-09-10 出光興産株式会社 水性金属加工油剤
EP0595770B1 (de) * 1992-10-30 1998-01-14 Ciba SC Holding AG Neue Dithiophosphate als Verschleissschutzadditive
DE4409961A1 (de) * 1994-03-23 1995-09-28 Rhein Chemie Rheinau Gmbh Metallfreie Dithiophosphorsäurederivate
US5715785A (en) * 1994-04-07 1998-02-10 Gregg, Jr.; George L. Method of lubricating machinery in the presence of an electrical charge
US5641731A (en) * 1994-11-04 1997-06-24 Ashland, Inc. Motor oil performance-enhancing formulation
US5962377A (en) * 1995-05-31 1999-10-05 Ashland Inc. Lubricant additive formulation
US6660695B2 (en) * 2002-03-15 2003-12-09 Infineum International Ltd. Power transmission fluids of improved anti-shudder properties
US10434520B2 (en) 2016-08-12 2019-10-08 Arr-Maz Products, L.P. Collector for beneficiating carbonaceous phosphate ores

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US2644002A (en) * 1951-08-29 1953-06-30 American Cyanamid Co Thiophosphatosuccinimides
US2767206A (en) * 1953-12-30 1956-10-16 Shell Dev Alicyclic esters of phosphoric acids
DE1074575B (de) * 1957-03-08 1960-02-04 Chemische Werke Albert, Wiesbaden-Biebnch Verfahren zur Herstellung von neutralen S Bicyclo-[2 2 1] heptyldi thiophosphorsaure 0 0-dialkylestern
GB1055094A (en) * 1965-02-23 1967-01-11 Shell Int Research Novel phosphorus-containing esters
US3406225A (en) * 1965-11-26 1968-10-15 Velsicol Chemical Corp Cyclic prosphorus acid esters
US3916017A (en) * 1969-12-24 1975-10-28 Ethyl Corp Polycyclic compounds
JPS4911226B1 (es) * 1970-06-24 1974-03-15
US3803270A (en) * 1971-08-04 1974-04-09 M Iliopulos Halo-substituted bicyclo alpha-hydroxyalkyl phosphonic acid diesters
US4035488A (en) * 1971-09-30 1977-07-12 Ciba-Geigy Corporation Insecticidal and acaricidal substituted phenyl thiophosphoric acid esters
US4067972A (en) * 1972-01-26 1978-01-10 Ciba-Geigy Corporation O-(Methyl or ethyl)-S-(propyl or butyl)-O-alkyl-(thio/sulfinyl/sulfonyl)-methylphenyl-thiophosphates
US3821322A (en) * 1972-09-08 1974-06-28 Ethyl Corp Polycyclic compounds
US3943202A (en) * 1972-11-03 1976-03-09 Ciba-Geigy Corporation O-methyl/ethyl-s-propyl/butyl-o-phenyl thiophosphates and dithiophosphates having an ether group or the phenyl ring
US3962105A (en) * 1975-03-25 1976-06-08 The Lubrizol Corporation Lubricating compositions
US4028258A (en) * 1975-12-03 1977-06-07 Texaco Inc. Alkylene oxide adducts of phosphosulfurized N-(hydroxyalkyl) alkenylsuccinimides
DE2556961A1 (de) * 1975-12-18 1977-06-30 Bayer Ag O-alkyl-o-phenylthionophosphonsaeureester, verfahren zu ihrer herstellung und ihre verwendung als insektizide
US4123526A (en) * 1975-12-24 1978-10-31 Stauffer Chemical Company Thionophosphate insecticide activators

Also Published As

Publication number Publication date
CA1308727C (en) 1992-10-13
WO1988000611A2 (en) 1988-01-28
US4729840A (en) 1988-03-08
ATE87027T1 (de) 1993-04-15
IN168375B (es) 1991-03-23
DE3784937T2 (de) 1993-06-24
WO1988000611A3 (en) 1988-03-24
AU7643487A (en) 1988-02-10
AU603819B2 (en) 1990-11-29
ES2010723A6 (es) 1989-12-01
ZA875004B (en) 1988-01-14
MX163959B (es) 1992-07-06
HK102793A (en) 1993-10-08
DE3784937D1 (de) 1993-04-22
JP2614882B2 (ja) 1997-05-28
JPH01503141A (ja) 1989-10-26
EP0321462A1 (en) 1989-06-28

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